土壤中铅的植物可利用性化学调控研究

针对重庆市蔬菜重金属污染现状，选取Pb为研究对象，通过盆栽试验，探讨石灰、腐殖酸、硫化钠对污染土壤中Pb活性的影响及Pb在植物体内的积累效应。研究结果表明，石灰、腐殖酸、硫化钠均能降低Pb的植物可利用性。不同石灰用量均能明显抑制Pb向植物迁移；在石灰的各种加入量中，10．0g／kg的加入量对Pb的抑制效果最明显，莴笋中Pb质量分数下降了35．7％；在腐殖酸的各种加入量中，2．67g/kg的加入量对Pb的抑制效果最明显，植物中Pb质量分数下降了23．0％；在硫化钠的各种加入量中，0．47g/kg的加入量对Pb的抑制效果最明显，植物体内Pb质量分数降低了23．8％。各种添加剂均能使植物根部Pb的分配系数下降，而茎、叶Pb的分配系数上升。     

南京城市土壤中重金属的化学形态分布

采取Tessier连续提取法，研究了南京市不同城区表层土壤中Fe,Mn,Cr,Ni,Co,V,Cu,Zn,Pb的化学形态分布。结果表明，南京城市土壤中Fe,Mn,Cr,Ni,Co,V,Zn,Pb以残渣晶格态为主，可交换态比例极低；Cu在城市道路旁的土壤中有机物结合态所占的比例最高，其他区域残渣晶格态所占的比例最高，与非城区自然土壤相比，主要来源于人为输入的Mn,Cu,Zn,Pb残渣晶格态所占的比例低，活性态比例大；Cr和主要来源于原土壤物质的Fe,Ni,Co,V在城市土壤与非城区自然土壤中各形态所占的比例相似，残渣晶格态比例大，活性态比例极低。     

稀土工业区土壤中钍形态的植物可利用性评价

土壤中钍的生物可利用性与其对生态环境的危害密切相关.分别采用小麦盆栽培养实验和连续萃取方法研究(Triticum aestivum L.)对土壤中钍的吸收及根际土壤和原质土壤中钍形态差别.结果表明,根际土壤中钍的质量分数较原质土壤低,根际土壤和原质土壤中钍的形态分布存在一定差别,根际土壤中非残留态量较原质土壤中高.利用吸附了钍的高岭土、蒙脱土、碳酸钙、无定形氧化铁、无定形氧化锰和腐殖酸等作为小麦水培实验基质材料,并采用连续萃取方法对钍各形态的植物可利用性进行了考察.吸附材料中钍对小麦吸收的贡献指数由大到小的顺序为:高岭土、碳酸钙、腐殖酸、无定形氧化铁、无定形氧化锰、蒙脱土.由各模拟材料结合的优势钍形态,钍各形态的小麦可利用性由大到小的顺序为:离子交换态、碳酸盐结合态、有机质吸附态、无定形铁锰氢氧化物共沉淀态、晶形铁锰氢氧化物结合态.     

改良剂对土壤Sb赋存形态和生物可给性的影响

采用室内土壤培养法研究不同改良剂(骨炭、生物调理剂、沸石、石灰、油菜秸秆、生物炭、堆肥和赤泥)对土壤Sb化学形态转化和生物可给性的影响.结果表明,除堆肥处理外,添加5%的其他7种改良剂均显著地提高了土壤的p H值,其中石灰处理p H最为明显.BCR分级提取表明,土壤Sb主要以残渣态形式存在.添加生石灰、骨炭和生物调理剂显著地提高了土壤Sb的移动性,而添加赤泥、生物炭和堆肥却显著地降低了土壤Sb的移动性.添加不同的改良剂对土壤Sb的生物可给性也有影响,但是受不同培养时间影响较大.培养2个月后,添加5%的堆肥、5%赤泥和5%生物炭处理导致土壤Sb的生物可给性含量分别比对照降低38%、23%和20%;而添加5%的石灰、5%油菜秸秆和5%的生物调理剂处理导致土壤Sb的生物可给性含量分别比对照提高1.07倍、1.06倍和1.11倍.堆肥、赤泥和生物炭是钝化Sb污染土壤的潜力材料.     

深圳市城市绿地土壤中重金属的含量及化学形态分布

对深圳市中心区城市绿地表层土壤(0-20cm)中Cu,Zn,Pb和Cd的含量、化学形态分布和迁移性进行研究.结果表明,土壤中Cu,Zn,Pb和Cd的含量分别为6.4-188.2(26.3)mg·kg-1,34.9-284.8(69.1)mg·kg-1,15.2-245.5(47.2)mg·kg-1和0.01-3.48(0.47)mg·kg-1.道路绿化带土壤中Cu,Zn和Pb的平均含量最高,在公园绿地土壤中Cd的平均含量最高.分别有75.6%,87.0%,98.8%和98.8%的土壤中Cu,Zn,Pb和Cd的含量超过广东省赤红壤的背景值,重金属在土壤中呈现明显的富集特征.土壤中Cu,Zn和Cd以残渣态所占比例最高,Pb以铁锰氧化物结合态最高.随着土壤中Cu,Zn,Pb和Cd含量的增加其残渣态所占比例降低,铁锰氧化物结合态或交换态所占比例增加,重金属活性增大.土壤中Cd迁移能力最强,迁移能力依次为Cd>Zn>Pb和Cu.     

沸石、磷矿粉和石灰对土壤铅锌化学形态和生物可给性的影响

通过室内土壤培养实验,研究添加沸石、磷矿粉和石灰3种改良剂对污染土壤Pb、Zn化学形态和生物可给性的影响.结果表明,土壤Pb主要以Fe-Mn氧化物结合态为主,而Zn主要以残渣态为主.改良剂对土壤Pb、Zn化学形态的影响随着培养时间的不同而不同.培养1个月时,2%磷矿粉和2%石灰处理可分别导致土壤醋酸(HOAC)提取态Pb含量下降76.0%和25.6%,3种改良剂处理导致土壤HOAC提取态Zn含量比对照处理降低6.1%～17.0%.培养2个月时,磷矿粉和石灰处理分别导致土壤HOAC提取态Pb含量下降62.8%和39.0%,石灰处理导致土壤HOAC提取态Zn含量下降34.6%.3种改良剂对土壤Pb、Zn的生物可给性也有影响,也随着土壤重金属种类和培养时间的不同而异.培养1个月时,沸石和磷矿粉可分别导致土壤Zn的生物可给性降低15.9%和14.9%,但培养2个月后3种改良剂对Zn的生物可给性却没有影响.研究结果表明,在酸性Pb、Zn复合污染农田土壤中均可以选择这3种改良剂来进行土壤改良,减少重金属的污染风险.     

PM10中重金属的提取方法及生物可利用性研究

分别运用模拟生物提取法与化学连续提取法对PM10标准参考样品城市源（NIST-1648A）和工业源（BCR-038）中6种重金属（Cd、Co、Cu、Mn、Ni、Pb）质量分数及赋存形态进行分析。其目标是验证2种提取大气固体颗粒物中重金属方法的有效性,并比较2种方法的优缺点,为将来提取PM10中重金属的方法选取提供依据。模拟生物提取法中,使用Gamble溶液模拟人体肺液对 PM10样品进行溶解,实验方法操作较为简单快捷;化学连续提取法中,不同溶解步骤则可确定重金属的不同赋存形态。在需要快速确定 PM10中某种重金属总量时,应优先使用模拟生物提取法。化学连续提取结果表明,城市源PM10中重金属赋存形态分布没有统一规律,工业源PM10中重金属多以残渣态存在。通过对2种来源的PM10样品中重金属生物可利用性分析,城市源的大气颗粒物对人体的毒性更大,其中标准参考样品城市源 PM10中生物可利用性较高的是重金属Cd（BIBio为61.65%±3.45%;BISE为69.02%±3.82%）和Cu,最低的是重金属Co和Pb;标准参考样品工业源PM10中重金属的生物可利用性最高的是Cd（BIBio为27.66%±1.52%;BISE为15.05%±2.13%）,而Ni、Co和Pb的生物可利用性较低。     

土壤中腐殖酸对外源农用稀土生物可利用性的影响

采用盆栽实验方法,研究了腐殖酸对稀土元素在土壤-植物体系中的迁移、富集和生物可利用性的影响,结果表明,在试验土壤红壤中,稀土元素主要富集在小麦根部,加入低浓度的腐殖酸后,促进了小麦对稀土元素的吸收：而高浓度的腐殖酸则抑制小麦对稀土元素的吸收,腐殖酸浓度过高时,对小麦生长产生毒害作用,同时发现,小麦中叶绿素含量与小麦中稀土含量存在相关关系。     

华南电子垃圾回收区农田土壤重金属污染及其化学形态分布

广东清远龙塘镇作为电子垃圾回收地区,已从事电子垃圾处置超过30年,可能给当地的农田土壤带来了严重的风险。为评价龙塘农田土壤中重金属污染程度,采集28个农田土壤样品,用于研究As、Cd、Co、Cr、Cu、Hg、Ni、Pb、Sn、Zn10种重金属含量及其不同存在形态。结果表明,与中国食用农产品产地环境质量标准比较,大多数当地农田土壤已在不同程度上受到重金属污染,85.7%的土壤样品中有一种或多种重金属的含量超过了相应的评价标准值。化学形态分析结果表明,除Hg外,人为来源的其她重金属更多地进入了可迁移形态部分(弱酸可溶态+可还原态+可氧化态),从而具有更高的毒害性和生物有效性,该电子垃圾处置区农田土壤已基本不适于食用农产品种植。大多数重金属在0.05或0.01水平上具有显著的相关性,这表明龙塘镇土壤重金属污染主要来源于不受控制的电子垃圾回收活动。对中国或其他国家具有类似的粗放式电子垃圾回收处置地区来说,有关龙塘镇农田土壤中重金属污染水平及其潜在的生物毒害性研究具有代表性意义。     

Effect of acid rain on the fractionation of heavy metals and major elements in contaminated soils

Acid rain is a serious environmental problem worldwide. In the present study, we investigated the effect of acid rain (1:1 equivalent basis H₂SO₄:HNO₃) at pH values of 2.0, 4.0 and 7.0 on the fractionation of heavy metals (Cd, Cu, Fe, Mn, Ni, Pb and Zn) and major elements (K, Na, Ca, and Mg) in contaminated calcareous soils over a 2084 h period. Heavy metals and major elements in soil samples were fractionated before and after 2084 h kinetic release using a sequential extraction procedure. Before kinetic studies the predominant fractions of K, Na, Ca, Mg, Cd and Ni were mainly associated with carbonate fraction (CARB), whereas Fe, Mn and Zn were associated with the Fe–Mn oxide fraction (Fe–Mn oxide). The highest percentage of Pb and Cu were found in the exchangeable (EXC) and organic matter (OM) fractions, respectively. After kinetic study using different simulated acid rain solutions, the major fractions of heavy metals (expect of Cu) and Na was the same as before release. Upon the application of different acid rain solutions, K and Mg were found dominantly in Fe–Mn oxide fraction, whereas Ca was in the EXC fraction. The results provide valuable information regarding metal mobility and indicated that speciation of metals (Cu and Zn) and major elements in contaminated calcareous soils can be affected by acid rain.     

The effects of application of agricultural wastes to firing range soil on metal accumulation in Ipomoea aquatica and soil metal bioavailability

The immobilisation of heavy metals in the soil of a 25-year-old active firing range using durian (Durio zibethinus L.) tree sawdust (DTS), coconut coir (CC) and oil palm empty fruit bunch (EFB) was investigated. The immobilisation effects were evaluated in terms of metal accumulation in water spinach (Ipomoea aquatica) and soil metal bioavailability. A pot experiment was conducted by amending the firing range soil with DTS, CC and EFB at application rates of 0%, 1% and 3% (w/w), respectively. All amendments increased the biomass yield and reduced the uptake of heavy metals in the plant tissue. Zn had the highest values of Bioconcentration Factor (BCF: 0.301–0.865) and Translocation Factor (TF: 1.056–1.883). Pb was the least-accumulated and transported metal in the plant tissues, with the BCF and TF values of 0.019–0.048 and 0.038–0.116, respectively. The bioavailable fraction of heavy metals in the firing range soil decreased following the application of the three agricultural wastes studied. DTS, CC and EFB did not cause toxicity symptoms in the water spinach over the pot experiment. Therefore, DTS, CC and EFB are considered promising immobilising agents for the remediation of metal-contaminated land.     

几种萃取剂对土壤中重金属生物有效部分的萃取效果

采用6种萃取剂:pH=7的0.01mol/L CaCl_2、pH=7.3的0.005mol/L DTPA+0.1mol/L TEA(三乙醇胺)+0.01mol/L CaCl_2O.1mol/L NaNO_3、0.43mol/L HOAc、pH=7的0.05mol/L EDTA和pH=4.65的0.5mol/L NH_4OAc+0.02mol/L EDTA浸取液.对污染土壤中的重金属Cu、Zn、Cd、Pb、的进行了萃取,并比较了萃取剂的萃取能力。实验结果表明,HOAc、EDTA以及NH_4OAc-EDTA萃取各种重金属的能力远远大于其它几种萃取剂的萃取能力,是比较理想的萃取剂。     

水稻不同生育期土壤砷形态分布特征及其生物有效性研究

采用田间原位试验和Tessier连续提取方法,在水稻（Oryza sativa L.）不同生育期研究了重金属复合污染高、中、低3个水平下的土壤砷的形态分布特征及其生物有效性。结果表明：在水稻不同生育期中,土壤各种形态的砷质量分数均表现为高污染水平土壤〉中等污染水平土壤〉低污染水平土壤;土壤中砷在水稻整个生育期均以残留态为主,占90%以上,交换态砷所占比例最低,不到0.5%;不同形态砷之间大都显著正相关,但是两种有效性较高的砷形态（交换态和碳酸盐结合态）与有机态砷之间的相关性较差;土壤砷的生物有效性表现为高污染水平土壤〉中等污染水平土壤〉低污染水平土壤,且随着水稻生育期的延长,土壤砷的生物有效性逐渐升高。     

重金属污染土壤的微生物响应

土壤微生物在受到重金属污染胁迫后，往往能够在区系组成、生理生化、遗传等方面对重金属作出响应。微生物对土壤重金属污染的上述响应可用来评价土壤的重金属污染状况，并为土壤污染的生物修复提供理论指导。文章对近年来有关重金属胁迫下土壤微生物响应的研究成果作系统综述。     

Assessment of toxicity of heavy metal contaminated soils by the toxicity characteristic leaching procedure

The concentrations of Cu, Zn, Pb and Cd in soils near a lead–zinc mine located in Shangyu, Zhejiang Province, China, were determined and their toxicity was assessed using the toxicity characteristic leaching procedure (TCLP) developed by the United States Environmental Protection Agency. The TCLP method is a currently recognized international method for evaluation of heavy metal pollution in soils. The available levels of Cu, Zn, Pb and Cd were 8.2–36, 23–143, 6.4–1367 and 0.41–2.2 mg kg⁻¹, respectively, while the international standards were 15, 25, 5 and 0.5 mg kg⁻¹, respectively. Soils around the mine were more polluted with Zn and Pb, followed by Cd and Cu. Moreover, the levels of heavy metals in the soils extracted by TCLP indicated that extraction fluid 2 was more effective than extraction fluid 1 in extracting the heavy metals from the polluted soils and there was a positive correlation between fluids 1 and 2. Available heavy metal contents determined by TCLP were correlated with soil total heavy metal contents.     

石灰氮对镉污染土壤中镉生物有效性的影响

以石灰作对比,在大田条件下研究了不同石灰氮用量对镉污染土壤中镉生物有效性的影响。结果表明,一定量石灰或石灰氮处理均能显著提高酸性土壤的pH值,降低污染土壤中有效态镉质量分数及水稻茎叶和糙米中的镉质量分数。与不施改良剂的对照相比,石灰施用量达到1 200 kg.hm-2时土壤pH值显著提高,土壤有效态镉质量分数降低12.6%（P〈0.05）,水稻茎叶和糙米中镉质量分数分别降低25.5%（P〈0.05）和28.3%（P〈0.05）;石灰氮施用量达到600 kg.hm-2时,土壤pH值显著高于对照,土壤有效态镉质量分数较对照降低10.9%（P〈0.05）,水稻茎叶和糙米中镉质量分数分别降低36.8%（P〈0.05）和33.0%（P〈0.05）。等量条件下（600 kg.hm-2）石灰氮对降低土壤镉有效性及水稻累积镉的效果相对优于石灰处理。因此,石灰氮与石灰一样可用于酸性重金属污染土壤的修复与改良,是一种极具潜力的土壤改良剂。     

Mitigation and remediation technologies for organic contaminated soils

Organic contaminated soils have become a widespread environmental problem, which may lead to a great threat to the quality of agricultural production and to human health. Physical, chemical, and biological technologies have been employed for the mitigation and remediation of organic contaminated soils. This paper reviews the progress of mitigation and remediation technologies for organic contaminated soils and suggests two different strategies for the mitigation of ’slightly-contaminated’ agricultural soils and the remediation of ‘heavily-contaminated’ soils/sites, respectively. On this basis, directions for future research in this field are suggested.     

Response of roselle (Hibiscus sabdariffa) to heavy metals contamination in soils with different organic fertilisations

The response of green roselle (Hibiscus sabdariffa) to Cu/Pb contamination and manure application in soil was investigated using pot experiments. Subsamples of a mineral soil were treated with increasing doses (0–500 mg kg^?1) of Cu/Pb only and/or amended (at 10% w/w) with poultry or swine manure. Roselle plants were grown, monitored for changes in growth rate and post-harvest aboveground dry biomass and tissue Cu/Pb concentrations were determined. The plants were typically greenish with linear growth profiles at all metal doses, indicating some level of tolerance. Dry biomass yields decreased as metal dose increased. Poultry manure enhanced roselle biomass yields better than swine manure. Tissue Cu/Pb concentrations increased linearly as metal doses increased in unamended soils; whereas nonlinear responses were observed in manure-amended soils. Soil-to-plant transfer factors, T _f (%) indicated that Cu (13≤T _f (% )≤60) was more phytoavailable to roselle than Pb (11≤T _f (% )≤20). Tissue metal concentrations were modelled from soil pH, organic matter, plant available and pseudototal metal; but the models appeared more reliable with plant available metal as a covariate than with pseudototal metal content. These observations may become useful whenever phytoextraction is the remedial option for soils moderately contaminated by toxic metals.     

Effect of red mud addition on the fractionation and bio-accessibility of Pb,Zn and As in combined contaminated soil

Using soil incubation experiments, the effect of red mud addition on the fractionation and bioaccessibility of Pb, Zn and As in combined contaminated soil was studied. The results showed that red mud addition could significantly decrease the concentration of HOAc-extractable Pb and Zn in soil. Compared with the control, 5% red mud addition could significantly reduce the concentrations of HOAc-extractable Pb and Zn in soil after 1, 2 and 3 months of incubation [62.5, 65.3 and 73.5% decrease (Pb), 56.7, 65.8 and 67.4% decrease (Zn)]. Whereas adding red mud could remarkably increase the concentrations of specific absorbed As and residual As in soil. The result of a simple bioavailability extraction test (SBET) indicated that all treatments with red mud addition markedly reduced the concentration of bioaccessible Zn but increased the concentration of bioaccessible As in soil, while having little effect on the concentration of bioaccessible Pb in soil. After 3 months incubation, all treatments including 1, 2 and 5% red mud addition reduced the concentration of bioaccessible Zn by 53.1–56.7% compared with the control, but increased the concentration of bioaccessible As by 1.81–6.25 times. The results suggested that red mud is an additive with potential for the remediation soil contaminated soil by combinations of heavy metals, although it should be added based on the different heavy metals in the soil. Combined use of red mud and hyperaccumulators to remediate heavy metal contaminated soil needs further study.